The present invention relates to the field of research for new catalyst compositions especially for use in polymerization processes. More particularly, this invention is directed toward an apparatus and method of performing homogeneous, and supported homogeneous catalysis employing compositions comprising a transition metal complex, a cocatalyst, and one or more polymerization modifier(s); as well as related techniques for rapidly creating and testing libraries of such compositions. This invention is also directed toward the use of certain catalyst compositions having improved properties in olefin polymerizations.
Combinatorial and other high through-put techniques have been used to rapidly screen large numbers of compounds for use in biological, organic and inorganic synthesis and research. Combinatorial materials science generally refers to the methods for creating a collection of chemically diverse compounds or materials and to methods for rapidly testing or screening this library of compounds or materials for desirable performance characteristics and properties. Areas for application of such combinatorial methods have included the discovery of inorganic compounds for use as high-temperature superconductors, magnetoresistive materials, luminescent compounds, and catalysts. Examples include U.S. Pat. Nos. 5,712,171, 5,776,359, 5,985,356, 6,004,617, 6,030,917, 6,045,671, 6,248,540, 6,326,090, 6,346,290, and 6,627,571, EP-A-978,499, and WO 00/40331.
In addition to the foregoing patent references, numerous academic papers have also disclosed combinatorial techniques, including: Senkan, Nature, vol. 394, pp. 350-353 (Jul. 23, 1998); Burgess et al., Angew. Chem. Int. Ed. Eng.,1996, 35, No. 2, pp. 220-222; Maier et al., Angew. Chem. Int. Ed. Ens., 1998, 37, No. 19, pp. 2644-2647; Reetz et al., Angew. Chem. Int. Ed. Eng., 1998, 37, No. 19, pp. 2647-2650; Angew. Chem. Int. Ed. Ens., 1998, 37, No. 17, pp. 2333-2336; Morken et al., Science, vol. 280, pp. 267-270 (Apr. 10, 1998); Gilbertson et al., Tetrahedron Letters, vol. 37, no. 36, pp. 6475-6478 (1996), and Boussie, et al., JACS, 2003, 125, 4306-4317.
In WO 00/40331 a combinatorial apparatus and method for evaluating homogeneous and supported homogeneous coordination polymerization catalysts including olefin polymerization catalysts employing a metal compound formed from a metal of Groups 3-15 of the Periodic Table of the Elements and one or more ligands is disclosed.
Although the foregoing and other references have advanced the art of combinatorial materials testing, still further improvements and advances are desired. In particular, more rapid techniques of screening candidate materials are desired. Moreover, while combinatorial techniques have been applied to the discovery of simple metal complex/cocatalyst combinations, more complex compositions including a polymerization modifier have not previously been treated to combinatorial techniques. More specifically, there remains a need to apply combinatorial techniques to rapidly screen and evaluate catalyst compositions comprising a polymerization modifier. Accordingly, there remains a need for a combinatorial method and apparatus for the rapid and reliable discovery and development of polymerization modifier containing compositions that is particularly adapted to use in olefin polymerizations.
Various transition metal complexes and catalyst compositions containing the same are previously known in the art. These complexes and methods for their preparation are described, inter alia, in U.S. Pat. Nos. 5,703,187, 6.013,819, 5,189,192, 5,532,394, 5,470,993, 5,486,632, 5,770,538, 5,495,036, 6,015,868, 6,153,776, 6,107,421, 5,866,704, 6,268,444, 6,034,022, 6,150,297, 6,515,155, 6,613,921, 5,972,822, 5,854,362, 5,892,076, 5,817,849, 6,084,115, 6,103,657, and 6,284,905 in publications 2003US 0204017, 2002US 0142912, WO 2000 020377, WO 2000/40331, and WO 2002 038628, and elsewhere.
Various cocatalysts, activators and activating techniques are similarly known in the art for use in combination with the foregoing metal complexes. Examples of references wherein cocatalysts are disclosed include the foregoing list of patents and publications as well as U.S. Pat. Nos. 5,064,802, 5,321,106, 5,721,185, 5,372,682, 5,783,512, 5,919,983, 6,344,529, 6,395,671, 6,214,760, and elsewhere.
Known compounds that have been previously disclosed for use in combination with transition metal complexes and cocatalysts in olefin polymerizations include alumoxanes, aluminum alkyls, and metal alkoxy or amide compounds, as disclosed in U.S. Pat. Nos. 5,453,410, 5,721,183, 6,074,977, 6,017,842, 6,214,760, 6,387,838, and elsewhere.